Lubricating composition



I Patented Mar. 18, 1947 2,417,433 LUBRICATING COMPOSITION Lester W.McLennan,

to Union Oil Angeles, Calif., a

El Cerrito, CaliL, aasignor Company of California, Los corporation ofCalifornia No Drawing. Application April 23, 1945, Serial No. 589,941

Claims. (Cl. 252-403!) This invention relates to lubricatingcompositions containing complex basic barium soaps and has specialreference to complex barium soap greases.

The object of the invention is to obtain all the benefits of suchlubricants and greases as are peculiar to complex barium soaps. Complexbarium soaps produce stable greases which have excellent melting pointand penetration characteristics, do not require hydration, and haveexceptional resistance to deterioration by the action of heat and by theaction of moisture. Another object 01' this invention is to provideprocesses for the manufacture of complex barium soap lubricants.

Complex barium soaps as used herein include products which aresubstantially neutral or substantially free from readily titratableexcess alkalinity, at least beyond a relatively small amount, theseproducts comprising a complex of a normal barium soap with a bariumsalt. The number of mols of barium salt combined with each moi of bariumsoap should be greater than 0.1 and, depending upon the particularsaponiflable material and upon the characteristics of the mineral oilemployed, it is preferred that the number of mols of barium salt per molof normal barium soap be between about 0.2 and 1.0, but it may be ashigh as 2.0 or even as high as 3.0

Normal barium soaps as used herein include those products which resultwhen one equivalent of barium hydroxide or other basically reactingbarium compound is reacted with one equivalent of a saponifiablematerial to form a soap, said soap being the normal barium salt of thehigh molecular weight organic acids present as such or desirable bysaponification from the saponifiabie material.

Examples oi saponiiiable materials containing high molecular weightorganic acids, present as such or readily derivable therefrom bysaponiflcation, include fats such as tallow, lard, oil, hog fat, horsefat, etc., high molecular weight organic acids such as stearic acid,oleic acid, the high molecular weight acids resulting from the oxidationof petroleum fractions (for example, paraffin wax and mineral oil),rosin and related products, high molecular weight naphthenic acids,sulfonic acids, etc., and saponifiabie waxes such as beeswax, sperm oil,degras, etc.

The present invention resides in lubricating compositions, especiallygreases which contain complex barium soaps which are substantiallyneutral or substantially free from readily titratable excess alkalinity.While the invention may be extended to freely fluid lubricants, such asDiesel engine lubricating oils containing small proportions of complexbasic soaps, it includes more particularly the use of such complexbarium soaps in proportions to thicken lubricating oils appreciably forthe purpose oi producing liquid greases or solid greases of varyingconsistencies. More particularly the invention resides in mineral oillubricants containing thickening proportions of complex barium soapswhere the molai ratio of barium salt to normal barium soap is betweenabout 0.2 and 1.0, although it extends to the upper limit aboveindicated, i. e., 3.0 and may be as low as 0.1. Especially stablecomplex barium soap greases have been found to have a molal ratio withinthe range of 0.3 to 0.9. The invention also comprises the method ofmaking such lubricants.

The invention also includes the use of basic soaps to produce lubricantsemploying high viscosity mineral oils, e. g., 50 or SAE grade or evenbright stocks as well as lower viscosity mineral oils, e. g., 10 or 20SAE grade. These mineral ols can be either of the Pennsylvania typewhich have a viscosity index of or higher, or

, the Mid-Continent type or even of the naphthenic type which have aviscosity index of 30 or lower. Greases or unusually good waterresistance have been prepared from oils containing as much as 25% byweight of asphalt or extracts derived from lubricating oil distillatesby treatment witn phenol, furi'urai, etc.

I have discovered that under appropriate conditions it is possible toform a complex having unique solubility characteristics in mineral,lubricating oils by reacting one mol of a normal barium soap with morethan about 0.1 mol of a barium salt. By the term barium salt" it ismeant to include preferably the simple reaction product resulting fromthe combination of one equivalent of barium hydroxide with oneequivalent of a mineral acid such as sulfuric acid, hydrochloric acid,orthophosphoric acid, pyrophosphoric acid, suifurous acid, carbonicacid, boric acid, thiosulfuric acid or of an organic acid of relativelylow molecular weight such as the monocarboxylic and polycarboxylic acidscontaining less than about 7 carbon atoms per molecule, such as formic,acetic, propionic, valeric, oxalic, malonic, succinic. etc., acids, thelow molecular weight alkyl and aryl sulfonic acids. the low molecularweight substituted carboxylic acids such as glyceric, giycoilic,thioglycollic, etc., acids, and the low molecular weight phenolio andthiophenolic compounds such as phenol, cresol, thiophenoi. etc. However,I may also employ acidic or basic salts in which one equivalent ofbarium hydroxide has been reacted with more or less than one equivalentof a mineral acid or low molecular weight organic acid.

Preferably, the bar um salt should be barium acetate or barium carbonateor a mixture of barium acetate and barium carbonate.

Desirably the complex barium soap is substantially neutral or free fromrelatively titratable excess alkalinity. By the terms "substantiallyneutral" or substantially free from readily titratable excessalkalinity" as used in this invention, are meant to include greaseshaving a free acid or free alkali content less than about the equivalentoi 5.0 mg. of KOH per gram of soap present. While it is prelerred thatthe greases oi. this invention be substantially neutral, under someconditions they may desirably contain a small amount of free acidity oralkalinity. For example, the finished greases may have a free alkalicontent, calculated as BaiOHlz, as high as about 0.5% by weight ofgrease or a free acid contentequivalent to about 2.0 mg. KOH per gram oigrease. Greases having a desired free acid or free barium hydroxidecontent can be produced by controlling the ratio of acidic materials tobasically reacting compounds as will be obvious to one skilled in theart.

Free alkalinity is measured in accordance with A. S. T. M. method oftest No. D-l28-40, section 18, except that titration is conducted in thecold and the titration is made directly with standard HCl solutionrather than by adding an excess of HCl solution and then back titratingwith alcoholic potassium hydroxide solution. Free acidity is measured inaccordance with A. S. T. M. method 01 test No. D-128-40, section 20.Briefly, the methods of test employed are as iollows:

A 10gram sample of the grease is weighed to the nearest tenth of a graminto a 250 ml. Erlenmeyer flask. To the flask is then added '75 ml. ofpetroleum ether and 50 ml. of 95% alcohol containing phenolphthaleinindicator, the alcohol having been previously made neutral as indicatedby the phenolphthalein indicator. The flask is stoppered and shakenvigorously in the cold until the grease has completely disintegrated andno lumps remain. The solution is then allowed to settle and tree alkalior free acid, as observed by the color the alcoholic layer, is titratedcarefully in the cold to the phenolphthalein end point with 0.5 normalHCl or alcoholic KOH, as required. Free alkalinity is calculated interms of Ba(0I-l):; free acidity in terms of oleic acid or acetic acid.Free alkalinity and free acidity may also be expressed in terms ofequivalent mg. of KOH per gram of grease.

While I do not wish to be limited by the theories advanced herein, itappears, however. that under the conditions as disclosed in thisinvention, it is possible for normal barium soap to form an associationcomplex" with a barium salt, this complex acting in many respects as asingle chemical component. For example, this complex has a differentsolubility in lubricating oil than either the normal barium soap or thebarium salt oi which it is composed. Further, although a given bariumsalt when added to a. normal barium soap grease as a filler. may bereadily extractable with water, the same barium salt combined with thenormal barium soap in the form oi a complex barium soap or the presentinvention is extractable either only with diihculty or not at all. Asanother indication of the novelty or my complex barium soap greases,attention should be called to the fact that whereas barium salts areusually relatively insoluble in mineral oils and when added as fillersto conventional normal soap greases, the latter are opaque and the saltscan be largely removed by passing through a flne mesh screen, my greasesare relatively transparent or translucent in appearance and none of thesalt is removable by mechanical means.

It is not meant to intimate that any given barium salt is the fullequivalent of any other barium-salt for modifying the characteristics ofa dispersion of normal barium soap in lubricating oil. In fact thecomplexes of various barium salts with a given normal barium soap varyover a wide range as regards their respective solubilities in a givenmineral lubricating oil. For example, a normal barium stearate-bariumcarbonate complex is more soluble in a given mineral oil than is anormal barium stearate-barium formate complex. Likewise, the lattercomplex appears to be more soluble than one formed from normal bariumstearate and barium acetate. Complexes of a given normal barium soapwith certain barium salts will possess just the proper characteristicsto form with a specific mineral oil a grease of the improved propertiesdescribed herein. Other complexes of the same normal barium soap withdiflerent barium salts will be either too soluble or insufllcientiysoluble to form desirable greases in the given mineral oil. In thelatter case it is possible and desirable to form excellent greasescoming within the scope of the present invention by mixing a complexwhich is too soluble in the specific mineral oil with one possessinginadequate solubility. The exact proportions of the two complexes to beused will depend upon the relative solubilities of the two complexes andcan be readily determined by one skilled in the greasemaking art.

It has also been noted that even though the final grease is to besubstantially anhydrous, a product of improved characteristics can oftenbe obtained by adding a small amount of water, for example, in the rangeof 0.1 to 3.0% by weight or even as high as 10% by weight of the greasecharge at a suitable temperature and subsequently increasing thetemperature to eflect substantially complete dehydration. The grease maybe at a temperature of about 210 F. or less when such water additionsare made, although temperatures as high as 230 F. or even as high as 300F. or higher may be used, and subsequent dehydration has beenaccomplished by heating to temperatures in the neighborhood of 250 F. orhigher when necessary. With certain saponiflable materials and bariumsalts the greases produced by the processes or the present inventionhave a granular appearance, but by employing the hydration-dehydrationtechnique, products of smooth buttery texture are obtained oftenaccompanied by an increase in consistency and melting point. Usually thehydration-dehydration technique to produce a final substantiallyanhydrous grease is most effective on a slightly acidic complex bariumsoap grease. Subsequently the grease can be adjusted to the desiredacidity or alkalinity by the addition of barium hydroxide or acid, asthe case may be. Further improvements in grease texture can likewiseusually be obtained by working the grease at temperatures below about200 F. and preferably below about F. prior to final packaging.

Although preferably the complex barium soap greases or this inventionare produced as sub- 6 stantially anhydrous products under someconcooled to room temperature, and if a grease, ditions a slight watercontent such as 0.01% to worked in the cold and drawn into packages.0.05 or even as high as 0.3% may be desirable Heating is preferablyconducted at atmospheric for om p p In p i n f this W r pressure in anopen bottle, however, the heating can be accomplished at any of a numberO St and reaction may b carried out in a closed kettle in the prepa aton o the grease s will be obvious under superatmospheric pressure. toone skilled in the art. For example, aft r y Another preferred method offorming the comdrating the grease as described above, the subplex bariumsoap lubricants of this invention sequent d hydr n n e stopped at a poincomprises mixing the saponifiable material, a which will give the watercontent required in the 10 small amount of mineral oil and the acidfinished p oduct or after complete dehydrati n acids, whose barium saltis desired in the complex the desired quantities of water can be addedan barium soap. Subsequently, barium hydrate in c porated in the greasan amount equivalent to the saponifiable material In order for t edesired Complex formation and acid is added to the mixture and thematepr ed w h t preferred temperature range, rial heated and agitated toeffect reaction and it is usually desirable that at least a small Ddehydration. During the dehydration stage addicentage of a polar solventin the neighborhood Mona] n may be added or n f the remaining of atleast 01% by W of the reacting mass oil required may be added subsequentto the debe Present Further appears that eferably hydration stage. Thelubricant is finally heated this polar solvent should be water, althoughunto a temperature f between about 2504350 F.

der some conditions the complex formation proor even as high as F"subsequently cooled to ceeds more readily in the presence of a mixtureroom temperature and if a grease worked in of water and glycerine, waterand glycol or some the cold to give the final product The hydra hydroxyor polyhydmxy Organic Compound Such hon-dehydration technique may beemployed at as ethyl alcoholr diethylene glycol Pref any of severalstages, as will be obvious to one erably the proportion of polar solventpresent Skilled in the art should be "K range of 05% to by W i It isalso possible to first form a normal barium of the reacting mass, butunder some conditions soap grease and Subsequently add barium hydrateSmaller quantitiesisuch as about 01% and higher followed by anequivalent amount of the acid quantities' Such as about 10% can be used-AS Whose barium salt it is desired to com lex with an indication of thedesirability of having at least the normal barium Soap Also it ispbssible to a Small percentage of a polar solvent m- I produce a complexbarium soap lubricant by addhave observed that, anhydrous normal banuming a barium salt dissolved, or at least partially soap when heated withanhydrous barium acetate dissolved) in water or other appropriate polarin the presence of oil at various temperatures 35 solvent as describedhereinabove to a normal famed the complex barium f greases barium soapgrease and subsequently heat to effect of my invention and in fact thebarium acetate formation of the complex barium soap remainedundissolved. On the other hand, when The farmatmn of the complex bariumSoap the Same mlxtutfle to Whlch had been added 5% lubricants of thisinvention generally require of Water was i and subsequently heated tomoderately high temperatures, preferably in the dehydrate f the i: thebarium range of about 225-325 F. However. under some Soap i f f gevldence of conditions it is desirable that the complex any free anumace m e mshed grease barium soap lubricants of this invention be heatedone of preferred 'i of forming the to temperatures as high as 400 F. oreven 550 F. complex barium soap lubiicants of the present prim, tocooling and Working in the co In invention is to charge to a kettleequipped with forming the normal barium scans and barium means forheating cooling, and agitation an salts by reacting a saponifiablematerial or an amount of banum hydrate (BMOHMBHZO) acidic material witha basically reacting comequjvalent to the number of mols of bariumpound. the base is added preferably as the hygzg gg zig gg gi g i gzg2225x2 22: droxide. Bai OH) 2, or as barium hydrate, although bariumSalt is desired in the finished grases is in some instances barium oxideor other basically added in an amount equivalent to that desired in iffig banun g g g be h the complex barium soap. After heating and age may ea e as a pow Ema gran agitating to effect reaction of this acid with the5 i or as an aqueous or slurry as barium hydroxide the saponifiablematerial is .Elther normal or 9Omp1ex.banum soap formatlon if: azi -2 2213 13}; g g gg g izgg wg of the lubr1cating oil to be used in thefinished saponifiable material is mixed with between lubricant, althoughinert low-boiling solvents may about one fom.m and twice its Weight ofthe be used under pressure and subsequently wa mineral oil to be presentin the finished lubricant. Grated to leave a pure complex banPm soap FAfter the introduction of the saponifiable maf powder can be dispersedterial, heating and agitation is continued to effect mmeral ml to formcomPlex barium Soap lubrisaponification and subsequently dehydration ofcant of the present mventlonthe complex barium soap. After dehydrationhas The amolfnt of complex harm-m Soap P be been completed or evenduring the dehydration corporated in the greases of this invention maystep, additional mineral oil may be added. be from about 5% to aboutalthough Finally, the lubricant is heated to a temperature Centrationsas low as about 2% and as high as of b t about 25 E and 350 or higher toabout may be desirable for certain special complete dehydration andobtain the desired Combinations and applicationscharacteristics and thencooled to approximately Complex arium o p may also be used in 200 F. Ifdesired, a small proportion of water relatively sm ll pr ort n t pro cel quid can be added at this time and subsequently greases and fluidlubricants, such as lubricating moved as described under thehydration-dehyoils for internal combustion engines, especially drationtechnique. Finally, the lubricant is 75 Diesel engines. The soapconcentrations in such applications are usually below about and arenormally in the range of 0.2% to about 2.0%.

Materials other than complex barium soaps may also be added to thelubricating compositions of this invention, such as water, alcohols, andother solvents, oxidation inhibitor, fillers, etc.. as desired.Additions of petrolatum and solvent extracts from lubricating oil stockshave been helpful in some instances. Oxidation inhibitors which may beadded to the grease include phenyl alpha naphthyiamine. tetramethyldiamino diphenyl methane, benzidine, etc.. and the amount thereof varyfrom about 0.001% to about 1.0% of the finished grease.

The following examples will serve as illustrations of the presentinvention:

EXAMILI I The following ingredients were charged to a steam jacketedgrease kettle of about i-barrei capacity equipped with means foragitation:

Pounds Tallow fatty acids (saponiflcation number:

208 mg. KOH per gram) 50 Naphthenic type oil (viscosity=350 SayboltUniversal seconds at 100 F.) 25

These materials were heated to approximately 180 F. and mixed to form ahomogeneous solution.

Separately. 25 pounds of barium hydrate, 20 pounds of water, and 8pounds of glacial acetic acid were mixed, then added to the kettle andfollowed by 27 pounds of barium hydrate the temperature in the kettlebeing between 180 and 200 F.

The kettle ingredients were continuously agitated and the temperaturegradually increased to effect reaction and dehydration. During thelatter part of the dehydration operation, '15 pounds of additionalnaphthenic-type oil was added so that the mixture would not become stiffand difficult to agitate at any time. Approximately 3 hours was requiredto complete the dehydration and at the end of this time the material inthe kettle exhibited a slight acidity. After the dehydration had beencompleted the kettle contents were heated to a temperature of 300 F. andmaintained at this temperature for a period of two hours. The materialwas then cooled to 200 F'., about one gallon of water added andthoroughly mixed in, and the temperature then increased to 280 F., toeffect dehydration. Finally as the complex barium soap grease cooledfrom 280 F., an additional 100 pounds of naphthenictype oil was gradedinto the batch and at a temperature of about 200 F., 1.4 pounds ofphenylalpha-naphthylamine, an oxidation inhibitor, was mixed in, thegrease further cooled to room temperature, worked in the cold. and drawninto packages.

The finished grease had ties:

the following proper- Composition Complex barium soap per cent by weight1 28.0

0.!5 moi barium acetate per mol of normal barium tailow fatty acid soap.

Physical characteristics A. B. '1'. M. penetration at I?F.--..--..--..-.. 317 Dropping point, "P 300 Resistance to boiling waterExcellent. not

affected Appearance --Smooth, transparent, slightly fibrous Exaurur 11 Acomplex barium soap grease was prepared in a manner similar to thatdescribed in Example 1, except that the naphthenic-typ oil employed hada viscosity at F. of 000 Saybolt Universal seconds and one moi of bariumacetate was employed for each moi of barium tailow fatty acid soap.Further, the grease was slightly alkaline, so prior to thehydration-dehydration operations, 2 pounds of tailow fatty acids wereadded and when the dehydration was almost complete, 1.14 pounds ofbarium hydrate was added in order that the finished product would besubstantially neutral.

The properties of this grease were as follows:

1 1 mol barium acetate per mol of normal barium tailow fatty acid soap.

Physical characteristics slightly fibrous Exsurns II! To a steamjacketed grease kettle equipped with means for agitation, 3400 parts byweight of barium hydrate and 650 parts by weight of glacial acetic acidwere charged and mixed to effect reaction. A solution of 3000 parts byweight of tailow fatty acids in 1500 parts by weight of anaphthenic-type oil (viscosity at 100 F.==600 Sayboit Universal seconds)was added and while continuing agitation the mixture was heated toeflect reaction and dehydration. During the final stage of thedehydration, an additional 4500 parts by weight of the naphthenic-typeoil was added.

The resultant mixture was alkaline so it was cooled to 200 F., 1000parts by weight of water and 100 parts by weight of tailow fatty acidsadded and the kettle contents again heated to about 280 F. to effectreaction and dehydration. An additional 9000 parts by weightnaphthenictype 011 was then added, the product cooled to roomtemperature, worked and drawn into packages.

The properties of this complex barium soap grease were as follows:

1 1 mol barium acetate per mol of normal barium tallo'w fatty acid soap.

A. S. T. M. penetration at 77 F 295 Dropping point. F 376 Resistance toboiling water -Excellent, not

affected ExAMrLz IV The following ingredients were weighed into akettle:

Parts by weight Prime tailow (saponification number=193) 56 Glacialacetic acid 4 Barium hydrate 46 Naphthenic type oil (viscosity=:600Saybolt Universal seconds at 100 F.) 56

While agitating, the material in the kettle was heated to 390 F. toeiiect reaction and dehydration. Subsequently, an additional 168 partsby weight or naphthenic-type oil was added and the material again heatedto 390 F. The contents of the kettle were then cooled to roomtemperature. and about one part by weight of water added. Whilecon"nuing agitation the grease was again heated to effect partialdehydration, subsequently cooled and worked to give a smooth,translucent product having an A. S. T. M. penetration at 77 F. or 189and a Ubbehlode dropping point of 295 F.

EXAMPLE V EXAMPLE VI A complex barium soap grease was prepared in mannersimilar to that described in Example 3, except that only one-half asmuch glacial acetic acid was employed and the remaining free bariumhydroxide was neutralized by passing carbon dioxide through the kettlecontents.

The resultant grease contained a complex barium soap comprising normalbarium soap in combination with both barium acetate and bariumcarbonate. This product had an A. S. 'I'. M. penetration at 77 F. of250. a Ubbehlode dropping point above 400 F., and showed excellentstability and resistance to the effects of boiling water.

EXAMPLE VII A complex barium soap grease was prepared in a mannersimilar to that described in Example 2. except that oil soluble sulfonicacids, such as are desired as by-products in the preparation ofpetroleum white oils, were used in place of the tallow fatty acids. Thisgrease was likewise a smooth, translucent product having a droppingpoint above 350 F. and resistant to the effects of boiling water.

The foregoing description of my invention is not to be taken as limitingmy invention but only as illustrative thereof since many variations maybe made by those skilled in the art without departing from the scope ofthe following claims.

I claim:

1. A lubricating composition comprising mineral oil and a. barium soapcomplex, the latter being an association complex comprising a normalbarium soap and a barium salt in which the ratio of equivalents ofbarium salt to equivalents of normal barium soap is between about 0.1and 3, said composition being substantially free from readily titratableexcess alkalinity.

2. A lubricating composition comprising mineral oil and a barium soapcomplex, the latter being an association complex comprising a normalbarium soap and a barium salt in which the ratio said composition beingsubstantially anhydrous and free from readily titratable excessalkalinity.

3. A lubricating composition according to claim 1, in which the ratio oiequivalents oi barium salt to normal barium soap is between about 0.2and 2.

4. A lubricating composition according to claim 1, in which the bariumsalt is a barium salt of a mineral acid.

5. A lubricating composition according to claim 1, in which the bariumsalt is a barium salt of low molecular weight organic a:id.

6. A lubricating composition according to claim 1, in which the bariumsalt is barium carbonate.

'7. A lubricating composition according to claim 1, in which the bariumsalt is barium acetate.

8. A lubricating composition according to claim 1. in which the bariumsoap complex is made by admixing normal barium soap and a barium salt ofmineral acid.

9. A lubricating composition according to claim 1, in which the bariumsoap complex is made by of a low molecular weight organic acid.

10. A lubricating composition according to claim 1. in which the bariumsoap complex is made by reacting normal barium soap, basically reactingbarium compound and an acid, the amount of acid being sufllcient toneutralize said basically reacting barium compound.

11. A lubricating composition according to claim 1, in which the bariumsoap complex is made by reacting normal barium soap, basicallyneutralize said basically reacting compound.

12. A lubricating composition according to claim 1, in which the bariumsoap complex is made by reacting normal barium soap, basically reactingbarium compound and a low molecular weight organic acid, The amount ofsaid acid being sufilcient to neutralize said basically reacting bariumcompound.

13. A lubricating composition according to claim 1 prepared by reactingapproximately equal chemical equivalents of a basically reacting bariumcompound and a saponifiable material containing high molecular weightorganic acids in the presence of mineral oil to yield a. normal bariumsoap, adding aqueous solution of a barium salt and then heating saidmixture to vaporize water therefrom.

14. A lubricating composition according to claim 1 prepared by heating asaponifiable material containing high molecular weight organic acids,low molecular weight organic acids and a basically reacting bariumcompound in the presence of mineral oil to yield a product containingsaid barium soap complex and then hydrating and dehydrating the product.

15. A lubricating composition according to claim 1 prepared by heating alow molecular weight organic acid, a basically reacting barium compoundand a mineral 011 containing high molecular weight organic acids toyield a product containing said barium soap complex, adding additionalmineral oil and then hydrating and dehydrating said product.

16. A lubricating composition according to claim 1, in which the bariumsoap complex comprises a normal barium soap, a barium salt oi a mineralacid and a barium salt of a low molecular weight organic acid.

17. A lubricating composition according to claim 1, in which the bariumsoap complex comprises a normal barium soap. barium carbonate and bariumacetate.

13. A lubricating composition according to claim 1 containing also asmall amount oi an oxidation inhibitor.

19. A lubricating composition according to claim 1 containing also asmall amount of phenyl alpha naphthylamine.

20. A method of preparing lubricants comprising reacting a saponiilablematerial, a basically reacting barium compound and low molecular weightorganic acid in the presence of mineral oil to yield a productcontaining a barium soap complex and then adding additional mineral oil,said barium soap complex having a ratio of equivalents of barium salt oflow molecular weight fatty acids to equivalents of barium soap of saidsaponiflable material between about 0.2 and 2.0 and being substantiallyfree irom readily titratable xcess alkalinity.

LESTER W. M LENNAN.

REFERENCES CITED The following references are of record in the die ofthis patent:

UNITED STATES PATENTS OTHER REFERENCES MoLennan, Methods 0! CompoundingBarium Greases, Their Properties, Uses. and Future, Article in NationalPetroleum News, Apr. 5, 1944, pages R234, R236, R238, and R239.

Certificate of Correction Patent No. 2 ,417,433.-

March 18, 1947.

LESTER W. McLENNAN It is hereby certified that error appears in thellows:

Letters Patent should be read with this numbered patent requiringcorrection as f0 desirable read derivable; and that the said correctiontherein that the same may conform to the record of the case in thePatent rinted specification of the above olumn 1, line 36, for the wordSigned and sealed this 8th day of JulyZA. D. 1947.

LESLIE FRAZER,

First Assistant Commissioner of Patents.

16. A lubricating composition according to claim 1, in which the bariumsoap complex comprises a normal barium soap, a barium salt oi a mineralacid and a barium salt of a low molecular weight organic acid.

17. A lubricating composition according to claim 1, in which the bariumsoap complex comprises a normal barium soap. barium carbonate and bariumacetate.

13. A lubricating composition according to claim 1 containing also asmall amount oi an oxidation inhibitor.

19. A lubricating composition according to claim 1 containing also asmall amount of phenyl alpha naphthylamine.

20. A method of preparing lubricants comprising reacting a saponiilablematerial, a basically reacting barium compound and low molecular weightorganic acid in the presence of mineral oil to yield a productcontaining a barium soap complex and then adding additional mineral oil,said barium soap complex having a ratio of equivalents of barium salt oflow molecular weight fatty acids to equivalents of barium soap of saidsaponiflable material between about 0.2 and 2.0 and being substantiallyfree irom readily titratable xcess alkalinity.

LESTER W. M LENNAN.

REFERENCES CITED The following references are of record in the die ofthis patent:

UNITED STATES PATENTS OTHER REFERENCES MoLennan, Methods 0! CompoundingBarium Greases, Their Properties, Uses. and Future, Article in NationalPetroleum News, Apr. 5, 1944, pages R234, R236, R238, and R239.

Certificate of Correction Patent No. 2 ,417,433.-

March 18, 1947.

LESTER W. McLENNAN It is hereby certified that error appears in thellows:

Letters Patent should be read with this numbered patent requiringcorrection as f0 desirable read derivable; and that the said correctiontherein that the same may conform to the record of the case in thePatent rinted specification of the above olumn 1, line 36, for the wordSigned and sealed this 8th day of JulyZA. D. 1947.

LESLIE FRAZER,

First Assistant Commissioner of Patents.

